CN108565412A - A kind of fluorocarbons blended anode pole piece and preparation method thereof - Google Patents
A kind of fluorocarbons blended anode pole piece and preparation method thereof Download PDFInfo
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- CN108565412A CN108565412A CN201810232242.1A CN201810232242A CN108565412A CN 108565412 A CN108565412 A CN 108565412A CN 201810232242 A CN201810232242 A CN 201810232242A CN 108565412 A CN108565412 A CN 108565412A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
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Abstract
A kind of fluorocarbons blended anode pole piece disclosed by the invention, including aluminium foil；One layer of positive active material coating has been respectively coated in the top and bottom of the aluminium foil；The positive active material coating is to coat the coating formed using the mixing material being made of fluorocarbons and metal oxide.In addition, the invention also discloses a kind of preparation methods of fluorocarbons blended anode pole piece.A kind of fluorocarbons blended anode pole piece disclosed by the invention and preparation method thereof, it can effectively solve the problems, such as that fluorinated carbon material surface energy is low, hydrophobicity is brought by force water-based system can not slurry, fluorinated carbon material and metal oxide can be uniformly blended into aqueous solvent and form anode active material slurry and ensure the solid content that anode active material slurry has, it has been obviously improved by the electric conductivity of the battery prepared by fluorocarbons anode pole piece, the overall performance for increasing substantially fluorocarbons lithium primary battery is conducive to the market application prospect for improving cell production companies product.
Description
Technical field
The present invention relates to battery technology fields, more particularly to a kind of fluorocarbons blended anode pole piece and preparation method thereof.
Background technology
Currently, fluorocarbons lithium primary battery is a kind of solid anode lithium primary battery, since its Theoretical Mass is reached than energy
It is highest in positive series to 2180Wh/kg, there is good high-temperature behavior and security performance, discharge platform is high and steady,
Self-discharge rate is low, is constantly subjected to greatly pay close attention to.
But due to fluorinated carbon material poorly conductive, cause the battery multiplying power of the system and cryogenic property very poor, to understand
Certainly this problem, the best way be by fluorocarbons and the metal oxide with certain electro-chemical activity and good rate capability into
Row mixing.Wherein, since the physical property characteristic of the metal oxides such as fluorinated carbon material and manganese dioxide (such as density, hydrophily) is poor
It is different very big, it is difficult to be mixed uniformly, therefore all traditional technique is mainly used to be prepared into thick electrode both at home and abroad, and apply
In electrical equipment of the discharge-rate less than 0.2C (electric discharge of 5 hour rates).
Although currently, by prolonged technical research, a kind of method, can effectively solve fluorocarbons not yet
The water-based system that material surface energy is low, hydrophobicity is brought by force can not slurry the problem of, fluorinated carbon material and metal can not be aoxidized
Object, which is mixed into aqueous solvent, to be formed anode active material slurry and ensures the solid content that anode active material slurry has, and is seriously affected
By the electric conductivity of battery prepared by fluorocarbons anode pole piece.
Therefore, it is low, hydrophobic fluorinated carbon material surface energy can effectively to be solved there is an urgent need to develop a kind of technology is gone out at present
The water-based system that property is brought by force can not slurry the problem of, fluorinated carbon material and metal oxide can be mixed into aqueous solvent and be formed
Anode active material slurry simultaneously ensures the solid content that anode active material slurry has, and has been obviously improved by fluorocarbons anode pole piece
The electric conductivity of prepared battery.
Invention content
In view of this, the object of the present invention is to provide a kind of fluorocarbons blended anode pole piece and preparation method thereof, Ke Yiyou
Effect solve the problems, such as fluorinated carbon material surface energy is low, hydrophobicity is brought by force water-based system can not slurry, can will be fluorinated carbon materials
Material and metal oxide, which are uniformly blended into aqueous solvent, to be formed anode active material slurry and ensures that anode active material slurry has
Solid content, be obviously improved by the electric conductivity of the battery prepared by fluorocarbons anode pole piece, increased substantially fluorocarbons lithium
The overall performance of one-shot battery is conducive to the market application prospect for improving cell production companies product, has great production real
Trample meaning.
For this purpose, the present invention provides a kind of fluorocarbons blended anode pole piece, including aluminium foil；The top and bottom of the aluminium foil
One layer of positive active material coating has been respectively coated；
The positive active material coating is to coat to be formed using the mixing material being made of fluorocarbons and metal oxide
Coating.
Wherein, the fluorocarbons includes fluorographite, fluorinated graphene, fluorinated carbon fiber, carbon fluoride nano-tube, fluorocarbons
It is one or more in microballoon, fluorinated reactive charcoal, fluorocarbons carbon black and fluorination bamboo charcoal.
Wherein, the quantity of fluorine atom and carbon atom ratio is (0.3~1.5) in the fluorocarbons：1.
Wherein, the metal oxide includes nickel dioxide NiO2, cobalt acid nickel Co2O4, copper oxide CuO, manganese dioxide
MnO2, cobalt oxide CoO, cobalt sesquioxide Co2O3With cobaltosic oxide Co3O4In it is one or more.
Wherein, the weight ratio between the fluorocarbons and metal oxide is 90:10~1:99.
In addition, the present invention also provides a kind of preparation method of fluorocarbons blended anode pole piece, include the following steps：
The first step：Fluorocarbons powder is mixed with organic solvent, obtains handling by organic solvent infiltration after stirring evenly
Powder；
Second step：Conductive agent and first binder are mixed, deionized water is added and is stirred evenly (as solvent), is led
Electric mixed glue solution；
Third walks：The described conductive mixed of preset weight percentage is added in the powder handled through organic solvent infiltration
Glue is closed, and is sufficiently stirred；
4th step：Continue to be gradually added metal oxide several times in the powder through organic solvent infiltration processing,
And it is sufficiently stirred；
5th step：Continue the remainder of the conductive mixed glue solution being gradually added several times and described be soaked through organic solvent
In the powder for moistening processing, and it is sufficiently stirred；
6th step：The second binder is continuously added, scattered mixed slurry is obtained；
7th step：The mixed slurry is uniformly coated to aluminium foil outer surface, and (aluminium foil is plus plate current-collecting body, specific using existing
Some coating equipments), after drying, obtain the fluorocarbons blended anode pole piece.
Wherein, the organic solvent includes：Alcohol, acetone, ethylene glycol, N-Methyl pyrrolidone NMP, ethylene carbonate
It is one or more in EC, propene carbonate PC, methyl ethyl carbonate EMC and dimethyl carbonate DMC.
Wherein, in the first step, the weight ratio between the organic solvent and fluorocarbons powder is (0.05~0.5)：1.
Wherein, the fluorocarbons includes fluorographite, fluorinated graphene, fluorinated carbon fiber, carbon fluoride nano-tube, fluorocarbons
It is one or more in microballoon, fluorinated reactive charcoal, fluorocarbons carbon black and fluorination bamboo charcoal；
The quantity of fluorine atom and carbon atom ratio is (0.3~1.5) in the fluorocarbons：1；
The metal oxide includes nickel dioxide NiO2, cobalt acid nickel Co2O4, copper oxide CuO, manganese dioxide MnO2, oxygen
Change cobalt CoO, cobalt sesquioxide Co2O3With cobaltosic oxide Co3O4In it is one or more.
Wherein, the weight ratio between the fluorocarbons powder and metal oxide is 90:10~1:99；
The first binder includes one in sodium carboxymethylcellulose (CMC), polyacrylate (PAA) and polyacrylonitrile
Kind is a variety of；
The conductive agent includes carbon black, Ketjen black, activated carbon, carbon nanotube CNT, carbon fiber VGCF, graphene
At least one of Graphene and graphite-like conductive agent；
Second binder includes styrene-butadiene latex SBR, sodium carboxymethylcellulose CMC, polyimides PI, polyacrylate
It is one or more in PAA, modified polyacrylate and polyacrylonitrile；
The solid content of the scattered mixed slurry is 20%~70%, and slurry viscosity is 1000cp~20000cp.
By the above technical solution provided by the invention as it can be seen that compared with prior art, the present invention provides a kind of fluorinations
Carbon blended anode pole piece and preparation method thereof can effectively solve the water that fluorinated carbon material surface energy is low, hydrophobicity is brought by force
Property system can not slurry the problem of, fluorinated carbon material and metal oxide can be uniformly blended into aqueous solvent and form positive-active
Compound paste simultaneously ensures the solid content that anode active material slurry has, and has been obviously improved prepared by fluorocarbons anode pole piece
The electric conductivity of battery increases substantially the overall performance of fluorocarbons lithium primary battery, is conducive to improve cell production companies production
The market application prospect of product, is of great practical significance.
Description of the drawings
Fig. 1 is a kind of flow chart of the preparation method of fluorocarbons blended anode pole piece provided by the invention；
Fig. 2 is with the preparation method of the preparation method of fluorocarbons blended anode pole piece provided by the invention, in embodiment
In the surface structure schematic diagram of battery that is assembled into of manufactured fluorocarbons blended anode pole piece；
Fig. 3 is with the preparation method of the preparation method of fluorocarbons blended anode pole piece provided by the invention, in embodiment
In surface structure schematic diagram of the battery that is assembled into of manufactured fluorocarbons blended anode pole piece after taking away shell；
Fig. 4 is with the preparation method of the preparation method of fluorocarbons blended anode pole piece provided by the invention, in embodiment
In in the battery that is assembled into of manufactured fluorocarbons blended anode pole piece, the winding position relationship of positive plate, negative plate and diaphragm
Schematic diagram；
Fig. 5 is with the preparation method of the preparation method of fluorocarbons blended anode pole piece provided by the invention, in embodiment
In in the battery that is assembled into of manufactured fluorocarbons blended anode pole piece positive plate structural schematic diagram；
Fig. 6 is with the preparation method of the preparation method of fluorocarbons blended anode pole piece provided by the invention, in embodiment
In in the battery that is assembled into of manufactured fluorocarbons blended anode pole piece negative plate structural schematic diagram；
Fig. 7 is with the preparation method of the preparation method of fluorocarbons blended anode pole piece provided by the invention, in embodiment
In the battery that is assembled into of manufactured fluorocarbons blended anode pole piece, it is bent with the obtained electric discharge of 0.4A constant-current discharges at room temperature
Line schematic diagram；
Fig. 8 is with the preparation method of the preparation method of fluorocarbons blended anode pole piece provided by the invention, in embodiment
In the battery that is assembled into of manufactured fluorocarbons blended anode pole piece, it is bent with the obtained electric discharge of 1.0A constant-current discharges at room temperature
Line schematic diagram.
Specific implementation mode
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction with the accompanying drawings with embodiment to this
Invention is described in further detail.
The present invention provides a kind of fluorocarbons blended anode pole pieces, including aluminium foil (as plus plate current-collecting body)；
One layer of positive active material coating has been respectively coated in the top and bottom of the aluminium foil；
The positive active material coating is (to be used as just using the mixing material being made of fluorocarbons and metal oxide
Pole active material) coat the coating formed.
In the present invention, in specific implementation, the fluorocarbons includes fluorographite, fluorinated graphene, fluorinated carbon fiber, fluorine
It is one or more in carbon nano tube, fluorination carbosphere, fluorinated reactive charcoal, fluorocarbons carbon black and fluorination bamboo charcoal.
In specific implementation, the quantity of fluorine atom and carbon atom ratio (i.e. the atomic ratio of F and C) is preferably in the fluorocarbons
(0.3~1.5)：1.
In the present invention, in specific implementation, the metal oxide is the substance for having electro-chemical activity, may include two
Nickel oxide NiO2, cobalt acid nickel Co2O4, copper oxide CuO, manganese dioxide MnO2, cobalt oxide CoO, cobalt sesquioxide Co2O3With four oxygen
Change three cobalt Co3O4In it is one or more.
In the present invention, in specific implementation, the weight ratio between the fluorocarbons and metal oxide is 90:10~1:
99。
In addition, referring to Fig. 1, the present invention also provides a kind of fluorocarbons blended anode pole piece preparation method, be used to prepare
The fluorocarbons blended anode pole piece that aforementioned present invention provides, this method specifically include following steps：
The first step：Fluorocarbons powder is mixed with organic solvent, obtains handling by organic solvent infiltration after stirring evenly
Powder；
Second step：Conductive agent and first binder are mixed, deionized water is added and is stirred evenly (as solvent), is led
Electric mixed glue solution；
Third walks：The described conductive mixed of preset weight percentage is added in the powder handled through organic solvent infiltration
Glue is closed, and is sufficiently stirred；
4th step：Continue to be gradually added metal oxide several times in the powder through organic solvent infiltration processing,
And it is sufficiently stirred；
5th step：Continue the remainder of the conductive mixed glue solution being gradually added several times and described be soaked through organic solvent
In the powder for moistening processing, and it is sufficiently stirred；
6th step：The second binder is continuously added, scattered mixed slurry is obtained；
7th step：The mixed slurry is uniformly coated to aluminium foil outer surface, and (aluminium foil is plus plate current-collecting body, specific using existing
Some coating equipments), after drying, obtain the fluorocarbons blended anode pole piece.
In the present invention, in specific implementation, the organic solvent includes：Alcohol, acetone, ethylene glycol, N- crassitudes
One in ketone (NMP), ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Kind is a variety of.
In specific implementation, in the first step, weight ratio between the organic solvent and fluorocarbons powder be (0.05~
0.5)：1.
In the present invention, in specific implementation, positive active material is formed by fluorocarbons and metal oxide together.
In the present invention, in specific implementation, the fluorocarbons includes fluorographite, fluorinated graphene, fluorinated carbon fiber, fluorine
It is one or more in carbon nano tube, fluorination carbosphere, fluorinated reactive charcoal, fluorocarbons carbon black and fluorination bamboo charcoal.
In specific implementation, the quantity of fluorine atom and carbon atom ratio (i.e. the atomic ratio of F and C) is preferably in the fluorocarbons
(0.3~1.5)：1.
In the present invention, in specific implementation, the metal oxide is the substance for having electro-chemical activity, may include two
Nickel oxide NiO2, cobalt acid nickel Co2O4, copper oxide CuO, manganese dioxide MnO2, cobalt oxide CoO, cobalt sesquioxide Co2O3With four oxygen
Change three cobalt Co3O4In it is one or more.
In the present invention, in specific implementation, the weight ratio between the fluorocarbons powder and metal oxide is 90:10~
1:99。
In the present invention, in specific implementation, the mixing plant for stirring is preferably planetary stirring machine, described planetary
Blender includes containing the big paddle of slow-speed and fast-turn construction high speed dispersion paddle, the speed of the big paddle of slow-speed be 10rpm~30rpm (rev/min
Clock), the speed of the fast-turn construction high speed dispersion paddle is 1000rpm~4000rpm, and the total time being sufficiently stirred is 1~20h
(hour).
In the present invention, in specific implementation, in second step, the first binder includes sodium carboxymethylcellulose
(CMC), one or more in polyacrylate (PAA) and polyacrylonitrile.
In the present invention, in specific implementation, in second step, the conductive agent can include carbon black, Ketjen black, activity
At least one of charcoal, carbon nanotube CNT, carbon fiber VGCF, graphene Graphene and graphite-like conductive agent.
In the present invention, in specific implementation, in the 6th step, second binder includes styrene-butadiene latex (SBR), carboxylic first
Base sodium cellulosate (CMC), polyimides PI, polyacrylate (PAA), modified polyacrylate and one kind in polyacrylonitrile or
It is a variety of.
In the present invention, in specific implementation, the number being repeatedly gradually added is preferably 2~5 times.
In the present invention, in specific implementation, in the 6th step, the solid content of the scattered mixed slurry is 20%~
70%, slurry viscosity is 1000cp~20000cp (centipoise).
In the present invention, in specific implementation, in the 7th step, the fluorocarbons blended anode pole piece after rolling,
Its thickness is preferably 50 μm~300 μm.
Based on the fluorocarbons blended anode pole piece that aforementioned present invention prepares, the present invention also provides a kind of batteries, should
Battery includes positive plate and negative plate, and diaphragm is provided between the positive plate and negative plate；
Wherein, the positive plate is the fluorocarbons blended anode pole piece, and the negative plate of the battery is the metal of conduction
Or alloy, the diaphragm are apertured polymeric film.
It should be noted that for the present invention, can continue to roll the fluorocarbons blended anode pole piece obtained,
Cut, obtain positive plate as battery, and the negative plate using metal or alloy as battery, apertured polymeric film as every
Film, to be assembled into battery.
In the present invention, in specific implementation, the metal includes lithium, sodium or magnesium, and the alloy includes containing lithium, sodium or magnesium
Alloy.
In the present invention, in specific implementation, the porous polymer membrane, material includes polythene PE, polypropylene PP
Or polyimides PI, i.e., the described porous polymer membrane is preferably using made of ethylene PE, polypropylene PP or polyimides PI
Multilayer composite membrane, and can also include using above-mentioned diaphragm as matrix and the painting of the functions such as surface coated with adhesive or ceramic coating
The compound diaphragm of layer.
In the present invention, in specific implementation, the structure of the battery is stacked or takeup type.
With reference to specific embodiment, to illustrate according to a kind of system of fluorocarbons blended anode pole piece provided by the invention
Preparation Method, the detailed process and prepared fluorocarbons for preparing fluorocarbons blended anode pole piece provided by the invention mix just
The superiority of pole pole piece and the battery of assembling.
Shown in Fig. 2 to Fig. 6, in embodiment, a kind of cylindrical lithium one-shot battery prepared by the present invention by pole group 1,
Shell 2, lid 3, electrolyte composition, wherein pole group 1 is by diaphragm 4, positive plate 5, negative plate 9, negative lug 10, terminal adhesive tape
11 compositions, positive plate 5 are made of collector 6, positive coating 7 and positive pole ear 8.
The battery of the present embodiment is prepared using following methods：
The first step：Make fluorocarbons blended anode pole piece：
First, the proportioning of fluorocarbons powder is carried out：By fluorographite (CF), manganese dioxide (MnO2), conductive agent conduction charcoal
Black SP, conductive agent acetylene black AB, binder sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) are according to 54:36:2:3:2:3
Weight ratio coordinated.
Then, slurry preparation is carried out：1.2kg fluorocarbons is added in the propene carbonate (PC, as organic solvent) of 0.2kg
It in powder, is mixed using planetary slurry equipment, it is 15rpm, jitter time 60min to adjust big paddle rotating speed.
Meanwhile the deionized water of the CMC of 0.044kg and 2.886kg being mixed with to obtain using planetary slurry equipment
Then the acetylene black of conductive agent conductive black SP, 0.066kg of 0.044kg is added in the CMC water mixed liquids that solid content is 15%
AB, it is 15rpm to adjust big paddle rotating speed, and it is 2000rpm, jitter time 60min that rapid dispersion, which starches rotating speed, obtains conductive epoxy glue
Liquid.
In the mixture of fluorocarbons and PC made from before the one third of conductive mixed glue solution is added, adjustment rotating speed is
Big paddle 15rpm, disperses 30min；Then 0.4kgMnO is added2Powder (1/2 powder weight), adjustment rotating speed are big paddle 15rpm, dispersion
30min；The half of remaining conductive mixed glue solution is added thereto again, continues to disperse 30min；By other 0.4kg MnO2Powder adds
Enter wherein, continues to disperse 30min using same rotational speed；Finally, remaining conductive mixed glue solution is all added, adjustment rotating speed is
It is 2000rpm that then big paddle adjustment of rotational speed is 15rpm by big paddle 15rpm, dispersion 10min, open rapid dispersion slurry rotating speed, point
Dissipate 60min；Next appropriate amount of deionized water is added and adjusts slurry viscosity in 15000cp or less；Finally, add 0.132kg,
The styrene-butadiene latex SBR water mixed liquids (the second binder) that solid content is 50%, it is 15rpm to open big paddle rotating speed, disperses 30min,
Slurry is completed to prepare；
Then, electrode coating is carried out：Using the aluminium foil of 15 μ m-thicks as plus plate current-collecting body, by the mixed slurry with single side
11.5mg/cm2Coated weight be coated uniformly on the two sides of aluminium foil, be divided to two sections of coatings, be all 410mm, two sections of coatings per segment length
Between be divided into 15mm, the coated length on two sides is identical；Then through rolling with shearing into 121 μ m thicks, the anode of 58mm width
Piece, and positive pole ear (preferably material is aluminium, thickness 0.07mm, width 4mm) is welded on the aluminium foil among two sections of powders,
Its structural schematic diagram is as shown in Figure 5；It is dried 12 hours using 150 DEG C, positive plate is made；
Second step：Make negative plate：Using 0.08mm thickness, 880mm long, 58mm moneys metal lithium sheet as negative pole currect collecting
Body, and 1 negative lug (material is copper, and size is 0.07mm thickness × 4mm wide) is pressed respectively at the both ends of negative current collector,
Structural schematic diagram is as shown in fig. 6, be made negative plate；
Third walks：Make battery pole group：Using 20 μ m-thicks polypropylene (PP) film as positive plate, negative plate every
Then film is wound into the cylindrical battery pole group that diameter is about 16.8mm, is finished up with diaphragm, stickup placed in the middle is one long at ending
The structural schematic diagram of rectangular terminal adhesive tape, the battery pole group is as shown in Figure 2, Figure 3, Figure 4；
4th step：Battery assembles：Obtained battery pole is assembled into the cylindrical type that outer diameter is 18mm, internal diameter is 17.7mm
In stainless steel casing, the bottom of negative lug and shell is welded, Upper gasket is added, the aluminium flake in positive pole ear and head cover is welded
It is connected together；Then battery assembling is completed in slot rolling, fluid injection, sealing；
5th step：Stand aging：Battery obtained above is stood 5 days at a temperature of 45 DEG C, measures battery open circuit voltage,
The battery that open-circuit voltage is 3.2V~3.5V is non-defective unit；
6th step：Discharge test：Six batteries are successively prepared using the above method, and six batteries are numbered respectively
For 1#, 2#, 3#, 4#, 5#, 6#.At ambient temperature, it is that three batteries of 1#, 2#, 3# are put with 0.4 ampere of (A) constant current by number
Electricity, blanking voltage 1.5V, the results are shown in Figure 7 for electric discharge；It is that other three batteries of 4#, 5#, 6# are permanent with 1 ampere (A) by number
Electricity is banished, blanking voltage 1.5V, the results are shown in Figure 8 for electric discharge.
It can be seen that from the discharge curve of Fig. 7 and Fig. 8：What the fluorocarbons blended anode pole piece prepared using this method was assembled
Number is six batteries of 1#, 2#, 3#, 4#, 5#, 6#, is discharged at room temperature with 0.4A, 1A, and it is existing voltage delay all do not occur
As the MnO excellent due to being mixed with high rate performance2The initial discharge platform of battery significantly improves, the initial electricity of 0.4A, 1A electric discharge
Pressure reaches 2.67V, 2.58V respectively；The consistency that battery discharges under two multiplying powers is all very good, three of number 1#, 2#, 3#
Capacity after battery is discharged with 0.4A electric currents is respectively 5.097Ah, 5.123Ah, 5.130Ah；Number is 4#, 5#, 6#'s
Capacity after three batteries are discharged with 1.0A electric currents is respectively 5.158Ah, 5.122Ah, 5.174Ah, and voltage platform
It is very consistent.
By the above technical solution provided by the invention as it can be seen that compared with prior art, fluorocarbons provided by the invention is mixed
Close anode pole piece preparation method, by advance using to the good organic solvent of fluorinated carbon material compatibility come to fluorocarbons into
Infiltration processing is gone, it may be difficult to which finely dispersed conductive agent is also pre-mixed with binder, to obtain conductive epoxy glue
Liquid, in preparation process, by the way that the big metal oxide distribution of density to be added in low density fluorination carbon active material, together
When substep be added conductive gelatin, using strength stirring in conjunction with high speed shearing disperse slurry mode, adequately to be mixed,
The mixed slurry finally obtained have the characteristics that each component be uniformly dispersed, solid content it is high.In addition, the fluorination prepared using this method
The battery that carbon blended anode pole piece is assembled into is lagged with no-voltage, big multiplying power discharging property is excellent and consistency of performance is good
Characteristic.
It, being capable of surface energy is extremely low, the extremely difficult fluorination disperseed in aqueous solvent for preparation method provided by the invention
Carbon material realizes good mixing in aqueous solvent together with metal oxide and disperses, not only easy to operate, environmentally friendly,
Production cost is low but also can directly use conventional lithium battery production equipment to realize large-scale production, has very high
Industry and commercial value.
Therefore, based on statement above it is found that compared with prior art, a kind of fluorocarbons mixing provided by the invention is just
Pole pole piece and preparation method thereof, can effectively solve fluorinated carbon material surface energy is low, hydrophobicity is brought by force water-based system can not
Fluorinated carbon material and metal oxide can be uniformly blended into aqueous solvent and form anode active material slurry simultaneously by the problem of slurry
Ensure the solid content that anode active material slurry has, has been obviously improved by the conduction of the battery prepared by fluorocarbons anode pole piece
Performance increases substantially the overall performance of fluorocarbons lithium primary battery, and the market for being conducive to improve cell production companies product is answered
With foreground, it is of great practical significance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of fluorocarbons blended anode pole piece, which is characterized in that including aluminium foil；
One layer of positive active material coating has been respectively coated in the top and bottom of the aluminium foil；
The positive active material coating is to coat the painting formed using the mixing material being made of fluorocarbons and metal oxide
Layer.
2. fluorocarbons blended anode pole piece as described in claim 1, which is characterized in that the fluorocarbons include fluorographite,
Fluorinated graphene, fluorinated carbon fiber, carbon fluoride nano-tube, fluorination carbosphere, fluorinated reactive charcoal, fluorocarbons carbon black and fluorination bamboo charcoal
In it is one or more.
3. fluorocarbons blended anode pole piece as described in claim 1, which is characterized in that fluorine atom and carbon are former in the fluorocarbons
The quantity ratio of son is (0.3~1.5)：1.
4. fluorocarbons blended anode pole piece as described in claim 1, which is characterized in that the metal oxide includes titanium dioxide
Nickel O2, cobalt acid nickel Co2O4, copper oxide CuO, manganese dioxide MnO2, cobalt oxide CoO, cobalt sesquioxide Co2O3With four oxidations three
Cobalt Co3O4In it is one or more.
5. fluorocarbons blended anode pole piece according to any one of claims 1 to 4, which is characterized in that the fluorocarbons and
Weight ratio between metal oxide is 90:10~1:99.
6. a kind of for producing the preparation method of fluorocarbons blended anode pole piece described in claim 1, which is characterized in that including with
Lower step：
The first step：Fluorocarbons powder is mixed with organic solvent, the powder by organic solvent infiltration processing is obtained after stirring evenly
Material；
Second step：Conductive agent and first binder are mixed, deionized water is added and is stirred evenly (as solvent), is obtained conductive mixed
Close glue；
Third walks：The conductive epoxy glue of preset weight percentage is added in the powder handled through organic solvent infiltration
Liquid, and be sufficiently stirred；
4th step：Continue to be gradually added metal oxide several times in the powder through organic solvent infiltration processing, and fills
Divide stirring；
5th step：Continue by the remainder of the conductive mixed glue solution be gradually added several times it is described through organic solvent infiltration at
In the powder of reason, and it is sufficiently stirred；
6th step：The second binder is continuously added, scattered mixed slurry is obtained；
7th step：The mixed slurry is uniformly coated to aluminium foil outer surface, and (aluminium foil is plus plate current-collecting body, is specifically used existing
Coating equipment), after drying, obtain the fluorocarbons blended anode pole piece.
7. preparation method as claimed in claim 6, which is characterized in that the organic solvent includes：Alcohol, acetone, ethylene glycol,
In N-Methyl pyrrolidone NMP, ethylene carbonate EC, propene carbonate PC, methyl ethyl carbonate EMC and dimethyl carbonate DMC
It is one or more.
8. preparation method as claimed in claim 6, which is characterized in that in the first step, the organic solvent and carbon fluoride powder
Weight ratio between body is (0.05~0.5)：1.
9. preparation method as claimed in claim 6, which is characterized in that the fluorocarbons include fluorographite, fluorinated graphene,
Fluorinated carbon fiber, carbon fluoride nano-tube, fluorination carbosphere, fluorinated reactive charcoal, fluorocarbons carbon black and fluorination bamboo charcoal in one kind or
It is a variety of；
The quantity of fluorine atom and carbon atom ratio is (0.3~1.5) in the fluorocarbons：1；
The metal oxide includes nickel dioxide NiO2, cobalt acid nickel Co2O4, copper oxide CuO, manganese dioxide MnO2, cobalt oxide
CoO, cobalt sesquioxide Co2O3With cobaltosic oxide Co3O4In it is one or more.
10. the preparation method as described in any one of claim 6 to 9, which is characterized in that the fluorocarbons powder and metal oxygen
Weight ratio between compound is 90:10~1:99；
The first binder includes sodium carboxymethylcellulose CMC, polyacrylate PAA and one kind or more in polyacrylonitrile
Kind；
The conductive agent include carbon black, Ketjen black, activated carbon, carbon nanotube CNT, carbon fiber VGCF, graphene Graphene and
At least one of graphite-like conductive agent；
Second binder include styrene-butadiene latex SBR, sodium carboxymethylcellulose CMC, polyimides PI, polyacrylate PAA,
It is one or more in modified polyacrylate and polyacrylonitrile；
The solid content of the scattered mixed slurry is 20%~70%, and slurry viscosity is 1000cp~20000cp.
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